CN105903469B - 一种用于压裂返排液催化湿式氧化过渡金属催化剂及其制备方法 - Google Patents
一种用于压裂返排液催化湿式氧化过渡金属催化剂及其制备方法 Download PDFInfo
- Publication number
- CN105903469B CN105903469B CN201610290063.4A CN201610290063A CN105903469B CN 105903469 B CN105903469 B CN 105903469B CN 201610290063 A CN201610290063 A CN 201610290063A CN 105903469 B CN105903469 B CN 105903469B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- transition
- cwo
- outlet liquid
- fracturing outlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 28
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000005406 washing Methods 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229910052804 chromium Inorganic materials 0.000 abstract description 9
- 238000005470 impregnation Methods 0.000 abstract description 7
- 239000003610 charcoal Substances 0.000 abstract description 6
- 239000002250 absorbent Substances 0.000 abstract description 5
- 230000002745 absorbent Effects 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000009279 wet oxidation reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- -1 Activated Carbon Pretreatment:Activated carbon 10 Chemical class 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical class [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本发明公开了一种用于压裂返排液催化湿式氧化过渡金属催化剂及其制备方法，该催化剂的成分以过渡金属的百分含量(即过渡金属质量占载体质量的百分数，下同)来计算：活性组分Cu(1～10％)，以Cr、Ce、Ni、Mn、Zn中的一种为辅助成分，其元素的质量百分数为1～5％；采用共浸渍法将过渡金属硝酸盐、硫酸盐、醋酸盐和氯化物负载于水洗、酸洗后的活性炭载体，经过干燥焙烧之后制得催化剂。本发明制得的催化剂其过渡金属元素分散均匀，孔隙结构较好；不含贵金属成分，成本低；催化效率高，适应性强，可在其他油气田废水、工业废水中推广应用。
Description
技术领域
本发明属于废水处理技术领域。涉及油气田压裂返排液的处理，具体指出一种催化湿式氧化处理压裂返排液用催化剂制备方法及其应用。本发明同时还指出基于该催化剂催化湿式氧化压裂返排液的处理方法。
背景技术
压裂技术在油气田钻井过程中的大量使用，不可避免的会产生大量的压裂返排液，压裂返排液由胍胶、杀菌剂、交联剂、粘土稳定剂、表面活性剂等组成，其有机物含量高，可生化性低，有机污染物主要有直链烷烃、醛类、酯类和苯等，属于石油行业较难处理的废水，若直接排放对土壤河流都会造成较大的污染。目前主要通过絮凝沉淀、氧化等物理化学方法处理压裂返排液，林海等(科学技术与工程(2014,19)155-158)采用破胶絮凝-预氧化-深度氧化工艺对COD总去除率达到79％；如涂磊等(西南石油大学学报(2007,S2)104-106)通过预氧化复合混凝-Fenton氧化-二次混凝工艺对COD总去除率达到84.75％。这些压裂废液处理工艺相对繁琐，深度处理较少，不仅成本较高，实际操作困难，且处理达标难度大。
催化湿式氧化为高浓度有机废水提供了一种新型高效的水处理技术，催化湿式氧化中所应用的催化剂不仅降低反应的活化能，而且在不降低处理效果的情况下，降低反应的温度和压力，提高氧化分解的能力，缩短反应的时间，提高反应效率，同时减少设备的腐蚀和降低成本。贵金属系列催化剂在催化湿式氧化处理废水过程中，具有较高的催化活性和稳定性。例如，中国专利CN104084217A公开的“一种氨氮废水催化湿式氧化处理的催化剂及其制备方法”，以活性炭作为载体，负载贵金属Pt、Pd、Ru、Rh中的一种和Fe、Co、Ni、Cu中的一种制备的催化剂。中国专利CN1498860A公开的“一种催化湿式氧化处理感光胶废水用催化剂及其应用”，以Pt、Ru、Pd、Rh中的一种及几种为活性组分制备催化剂应用于感光胶废水处理。中国专利CN102039128A公开的“废水的催化湿式氧化催化剂及其制备方法”，以Pt、Pd、Ru、Tr或Rh中的至少一种金属和Bi、Ba、Mg、B、V、Mo或稀土中至少一种金属负载于TiO2、Al2O3、SiO2或ZrO2载体制备催化剂。它们作为催化剂活性组分不仅处理成本增加，并且贵金属负载的TiO2、ZrO2等催化剂表现出来的催化活性并不理想。特别是贵金属应用于实际废水处理容易钝化或者中毒，降低其催化活性。
目前国内外催化湿式氧化研究对象更多趋向于模拟废水，Stanko等(Applied Catalysis B:Environmental 28(2000,2)113-125)研究了CuO-CeO2催化湿式氧化处理纯物质苯酚，Albin Pintar等(Applied Catalysis B:Environmental84(2008,1)30-41)研究了Ru/TiO2催化湿式氧化纯物质甲酸、乙酸、苯酚。Cédric Lousteau等(Catalysis Today 41(2015)80-85)研究了贵金属催化湿式氧化纯物质氨。这些研究虽然对溶液中的有机物具有一定的去除效果，但是针对的有机溶液都是模拟废水，没有用于实际废水的处理。如果用于实际废水处理可能会存在催化剂中毒或者催化效率降低等问题。本发明制备一种过渡金属催化剂催化湿式氧化油气田压裂返排液更加具有推广价值，现场可实施性更强。
发明内容
本发明的目的在于制备一种用于压裂返排液催化湿式氧化催化剂，该催化剂活性组分及辅助成分均为过渡金属，催化性能好，克服了现有催化湿式氧化催化剂成本高、实际废水处理过程中易失活等问题。
本发明技术方案如下：
本发明所述一种用于压裂返排液催化湿式氧化过渡金属催化剂，该催化剂以Cu(1～10％)为活性组分，以Cr、Ce、Ni、Mn、Zn中的一种为辅助成分，其元素的的质量百分数为1～5％，负载于活性炭载体。
本发明提供的以活性炭为载体的湿式氧化催化剂的制备方法是采用共浸渍法将过渡金属Cr、Ce、Ni、Mn、Zn、Cu中的一种或几种硝酸盐、硫酸盐、醋酸盐或氯化物溶液负载于活性炭表面，催化剂制备方法：
(1)活性炭预处理：取活性炭用去离子水浸渍10～12h，并不断搅拌至上层液体澄清，把清洗后的活性炭沥干，在95～110℃干燥10～12h，最后在200～400℃焙烧1～2h；
(2)活性炭活化：将第一步得到的活性炭用20～40％的硝酸溶液，在60～80℃的条件下回流1～2h；
(3)过渡金属负载：将第二步得到的活性炭浸渍在一定浓度的过渡金属溶液中，并置于40～60℃水浴中，连续搅拌1～3h，过滤静置1～2h；
(4)将第三步得到的活性炭在空气气氛、常压下置于95～110℃的烘箱中干燥10～12h；
(5)将第四步得到的活性炭置于400～700℃马弗炉焙烧2～4h，常温下冷却，即为本发明用于压裂返排液催化湿式氧化过渡金属催化剂。
本发明所述催化湿式氧化的过渡金属催化剂置于400～700℃马弗炉焙烧2～4h，过渡金属催化剂孔隙结构较好，具有较好的催化性能。
本发明所述催化湿式氧化的过渡金属催化剂中过渡金属在活性炭载体上分散性良好，过渡金属很少聚集形成晶体，且过渡金属之间表现强烈的相互作用。
本发明所述催化湿式氧化的过渡金属催化剂对压裂返排液中芳香类、长链类有机物氧化还原效果明显，且过渡金属离子渗滤较少。
本发明所述催化湿式氧化的过渡金属催化剂在压裂返排液处理过程中表现较好的催化性能，适应性强，因此可在其他油气田废水、工业废水中推广应用。
附图说明
图1预处理活性炭SEM图像及EDS分析结果
图2不同催化剂XRD图谱
图3制得1％Cu 1％Cr/AC催化剂SEM图像及EDS分析结果
具体实施方式
以下是本发明的具体实施例，对本发明的技术方案做进一步描述，但是本发明的保护范围并不限于这些具体实施例。凡是不背离本发明构思的改变或等同替代均包括在本发明的保护范围之内。
实施例1：
催化剂制备
载体预处理：取活性炭用去离子水浸渍10～12h，并不断搅拌至上层液体澄清，目的是去除催化剂载体在运送过程中吸附的灰尘等杂质以及由于磨损产生的粉末活性炭；把清洗后的活性炭沥干，并在110℃干燥12h，最后在300℃焙烧2h，以去除活性炭吸附的有机物。
将1.0972g Cu(NO3)2·3H2O和1.43g Ni(NO3)2·6H2O溶于20mL去离子水中制得过渡金属浸渍液，加入5g预处理之后的活性炭载体，在40℃水浴条件下连续搅拌1h，充分浸渍。把浸渍后的活性炭沥干，在105℃条件下干燥2h，将干燥后的活性炭置于480℃马弗炉中焙烧2h，焙烧后的活性炭冷却，制得1％Cu 1％Ni/AC催化剂。
催化剂活性评价方法
制得的催化剂在序批式高温高压反应釜中进行反应，催化剂用量1g，压裂废水中COD为3400mg/L，TOC为1975mg/L。实验条件：溶液pH为7，反应温度250℃，反应压力5.5MPa，反应时间2h。通过《水质化学需氧量的测定重铬酸盐法》GB 11914-89分析COD，通过岛津TOC-VCPH测定TOC，结果如表1所示。
实施例2：
将1.0972g Cu(NO3)2·3H2O和0.8099g Zn(CH3COO)2溶于20mL去离子水中制得过渡金属浸渍液，其余催化剂制备方向同实施例1，制得1％Cu 1％Zn/AC催化剂。催化剂活性评价条件同实施例1，结果如表1所示。
实施例3：
将1.0972g Cu(NO3)2·3H2O和0.8879g MnSO4·H2O溶于20mL去离子水中制得过渡金属浸渍液，其余催化剂制备方向同实施例1，制得1％Cu 1％Mn/AC催化剂。催化剂活性评价条件同实施例1，结果如表1所示。
实施例4：
将1.0972g Cu(NO3)2·3H2O和1.4788g CrCl3·6H2O溶于20mL去离子水中制得过渡金属浸渍液，其余催化剂制备方向同实施例1，制得1％Cu 1％Cr/AC催化剂。催化剂活性评价条件同实施例1，结果如表1所示。
实施例5：
将1.0972g Cu(NO3)2·3H2O和0.8099g Ce(NO3)3·6H2O溶于20mL去离子水中制得过渡金属浸渍液，其余催化剂制备方向同实施例1，制得1％Cu 1％Ce/AC催化剂。催化剂活性评价条件同实施例1，结果如表1所示。
表1不同过渡金属催化剂催化湿式氧化压裂返排液性能
通过表1可知，实施例1-5制得的催化剂对压裂返排液都具有较好的处理效果，其中实施例4处理压裂返排液，COD去除率达94.7％，TOC去除率达96.8％。
实施例6：
将1.0972g Cu(NO3)2·3H2O和1.4788g CrCl3·6H2O溶于20mL去离子水中制得过渡金属浸渍液，加入5g预处理之后的活性炭载体，催化剂浸渍及干燥方法同实施例1，将干燥后的活性炭置于550℃马弗炉中焙烧2h，制得1％Cu1％Cr/AC催化剂。催化剂活性评价条件同实施例1，结果如表2所示。
实施例7：
催化剂制备方法同实例6，将干燥后的活性炭置于620℃马弗炉中焙烧2h，制得1％Cu 1％Cr/AC催化剂。催化剂活性评价条件同实施例1，结果如表2所示。
实施例8：
催化剂制备方法同实例6，将干燥后的活性炭置于690℃马弗炉中焙烧2h，制得1％Cu 1％Cr/AC催化剂。催化剂活性评价条件同实施例1，结果如表2所示。
表2焙烧温度对1％Cu 1％Cr/AC催化湿式氧化压裂返排液的影响
通过表2可知，实施例4、6-8制得的催化剂对压裂返排液都具有较好的处理效果，其中实施例4处理对压裂返排液，COD去除率达94.7％，TOC去除率达96.8％。
Claims (2)
1.一种用于压裂返排液催化湿式氧化过渡金属催化剂，其特征在于：催化剂制备方法：(1)取洗涤、酸化后的活性炭浸渍于过渡金属盐溶液中，并置于40～60℃水浴中，连续搅拌1～3h，过滤静置于95～110℃的烘箱中干燥10～12h；(2)将步骤(1)制得的活性炭置于480℃马弗炉焙烧2～4h，制得Cu M/AC催化剂，即为本发明用于压裂返排液催化湿式氧化过渡金属催化剂；M表示过渡金属Cr。
2.根据权利要求1所述的一种用于压裂返排液催化湿式氧化过渡金属催化剂，其特征在于：在催化湿式氧化处理压裂返排液按如下条件进行操作：反应温度：200～260℃，反应氧分压：1～3MPa，反应总压5～7MPa，转速120～180r/min，反应pH：4～7。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290063.4A CN105903469B (zh) | 2016-05-05 | 2016-05-05 | 一种用于压裂返排液催化湿式氧化过渡金属催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290063.4A CN105903469B (zh) | 2016-05-05 | 2016-05-05 | 一种用于压裂返排液催化湿式氧化过渡金属催化剂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105903469A CN105903469A (zh) | 2016-08-31 |
| CN105903469B true CN105903469B (zh) | 2018-04-03 |
Family
ID=56752451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610290063.4A Active CN105903469B (zh) | 2016-05-05 | 2016-05-05 | 一种用于压裂返排液催化湿式氧化过渡金属催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105903469B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203179A (zh) * | 2020-01-15 | 2020-05-29 | 清创人和生态工程技术有限公司 | 一种可再生含酚有机废水催化吸附材料的制备方法及应用 |
| CN115475619B (zh) * | 2021-06-16 | 2024-03-29 | 中国石油化工股份有限公司 | 一种湿式氧化催化剂及其制备方法和应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2096891A1 (en) * | 1992-05-22 | 1993-11-23 | Karl Tze-Tang Chuang | Catalytic wet air oxidation in the presence of hydrogen peroxide |
| CN102049256A (zh) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | 一种废水处理催化剂及其制备方法 |
| CN103041818A (zh) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | 催化湿式氧化催化剂的制备方法和有机废水处理方法 |
| CN104556486A (zh) * | 2015-01-05 | 2015-04-29 | 中国石油大学(北京) | 一种油气田压裂废液的处理方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58114732A (ja) * | 1981-12-28 | 1983-07-08 | Osaka Gas Co Ltd | 触媒の再生法 |
-
2016
- 2016-05-05 CN CN201610290063.4A patent/CN105903469B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2096891A1 (en) * | 1992-05-22 | 1993-11-23 | Karl Tze-Tang Chuang | Catalytic wet air oxidation in the presence of hydrogen peroxide |
| CN102049256A (zh) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | 一种废水处理催化剂及其制备方法 |
| CN103041818A (zh) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | 催化湿式氧化催化剂的制备方法和有机废水处理方法 |
| CN104556486A (zh) * | 2015-01-05 | 2015-04-29 | 中国石油大学(北京) | 一种油气田压裂废液的处理方法 |
Non-Patent Citations (2)
| Title |
|---|
| "Catalytic oxidation of pulping effluent by activated carbon-supported heterogeneous catalysts";Bholu Ram Yadav等;《Environmental Technology》;20151027;第37卷(第8期);第1018-1025页 * |
| "Catalytic Wet Oxidation of Ferulic Acid (a Lignin Model Compound) in the Presence of Non-noble Metal Based Catalysts at Mild Conditions";Bholu Ram Yadav等;《Environmental Technology》;20140915;第252卷;185-193页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105903469A (zh) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jing et al. | Progress of catalytic wet air oxidation technology | |
| CN104084217B (zh) | 一种氨氮废水催化湿式氧化处理的催化剂及其制备方法 | |
| Nadeem et al. | Coal fly ash-based copper ferrite nanocomposites as potential heterogeneous photocatalysts for wastewater remediation | |
| CN104923229A (zh) | 用于类Fenton技术的活性炭催化剂及其制备和应用 | |
| CN104646020A (zh) | 一种臭氧催化剂及制备方法 | |
| CN103523891B (zh) | 含有机物废水催化湿式氧化的方法 | |
| CN110152667B (zh) | 一种铁屑表面改性形成γ-FeOOH的方法 | |
| CN105854900A (zh) | 一种无害化处理氨氮废水的催化湿式氧化催化剂及其制备方法 | |
| CN105233838B (zh) | 一种以活化膨润土为载体的o3/h2o2催化剂的制备方法、催化剂及其应用 | |
| CN112410037B (zh) | 一种土壤污染治理复合功能材料及其制备方法 | |
| CN105903469B (zh) | 一种用于压裂返排液催化湿式氧化过渡金属催化剂及其制备方法 | |
| CN104415754A (zh) | 一种固定化多相芬顿催化剂的合成方法 | |
| CN109529868A (zh) | 一种铁锰钴共掺杂负载型芬顿催化剂、制备方法及其应用 | |
| CN106512988B (zh) | 一种分子筛负载型MnO2-ZnO臭氧催化剂及其制备方法 | |
| CN107537459A (zh) | 一种处理生物难降解工业有机废水催化剂的制备方法 | |
| Zhu et al. | Hydrothermal preparation of NiO/La–NaTaO3 composite photocatalyst for degradation of ammonium dibutyl dithiophosphate wastewater | |
| Li et al. | Peroxymonosulfate activation with Co3O4 by microstructure engineering for efficient degradation of tetracycline: Efficiency, mechanism and stability | |
| Saroha | Effectiveness of fresh and used supported noble and non-noble metal based catalysts for industrial organic raffinate oxidation by catalytic wet air oxidation at low operating parameters | |
| CN110813305B (zh) | 一种铁屑表面改性剂及制备α-Fe(1-x)CrxOOH活性层的方法 | |
| CN106552644A (zh) | 难生化废水用臭氧催化剂及其制备方法 | |
| CN107469818A (zh) | CaZrO3载体的制备方法及将贵金属负载于载体上的催化剂及其制备方法与应用 | |
| CN107552046A (zh) | 催化湿式氧化处理丙烯酸废水催化剂及其制备方法和应用 | |
| CN105772050B (zh) | 一种制备吸波催化剂及其降解有机废水的方法 | |
| CN105236480B (zh) | 一种独特形貌的HCOOBiO纳米晶及其制备方法 | |
| CN105478118B (zh) | 一种Cu/TiO2纳米棒催化剂及其制备方法和在废水湿式氧化中的应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211228 Address after: 8 Tashan Road, Karamay, Xinjiang Uygur Autonomous Region 834000 Patentee after: Karamay Yurong Co.,Ltd. Address before: 610500, Xindu Avenue, Xindu District, Sichuan, Chengdu, 8 Patentee before: SOUTHWEST PETROLEUM University |